Contact agents for converting ethylenically unsaturated hydrocarbons to carbonylic compounds



United States Patent 3,379,651 CONTACT AGENTS FOR CONVERTING ETH-YLENICALLY UNSATURATED HYDROCAR- BONS T0 CARBONYLIC COMPOUNDS CharlesWesley Hargis and Howard Seth Young, both of PD. Box 511, Kingsport,Tenn. 37662 No Drawing. Continuation-impart of abandoned applicationSer. No. 163,079, Dec. 29, 1961. This application Nov. 28, 1966, Ser.No. 597,211

Claims. (Cl. 252437) ABSTRACT OF THE DISCLOSURE Process for convertingethylenically unsaturated hydrocarbons to car-bonylic compounds in thepresence of a novel catalyst composition comprising a titania orzirconia supported mixture of at least one of molybdenum trioxide,molybdenum heteropolyacid and a salt of molybdenurn heteropolyacidtogether with a second component of platinum or palladium or compoundsthereof. The process is useful for preparing products which are useableboth for solvent extraction purposes and for the preparation of wargasses, resins, glycerin, polyurethane, polyester resins and the like.

This application is a continuation-in-part of our copending applicationSer. No. 163,079, filed Dec. 29, 1961 and now abandoned.

This invention relates to the preparation of carbonylic compounds. Moreparticularly, this invention relates to the conversion of ethylenicallyunsaturated hydrocarbons to carbonylic compounds at relatively mildconditions of temperature and pressure. In a specific aspect, thisinvention relates to the preparation of carbonylic compounds atrelatively mild reaction conditions in the presence of contact agentscontaining platinum or palladium metals or compounds of these metals.

It is known that carbonylic compounds can be prepared by oxidizingethylenically unsaturated hydrocarbons, for example, ethylene, propyleneor butene, in the presence of noble metals. However, such processessuffer from a number of disadvantages and are not, therefore, whollydesirable oxidation processes for the preparation of carbonyliccompounds. For example, the use of noble metals as major activecomponents in such processes places a heavy cost burden on theseprocesses making them economically unattractive. Furthermore, in liquidphase operation particularly, these systems tend to sufier a reductionin oxidation state with consequent plating out or precipitation ofinsolubles which give rise to processing complications, for example,complications in stirring, conveying and reconstitution of noble metalcomponents. Moreover, prior art processes for converting ethylenicallyunsaturated hydrocarbons to carbonylic compounds have, for the mostpart, employed rather severe reaction conditions. It is obvious,therefore, that the state of the art will be greatly enhanced byproviding a process for the conversion of ethylenically unsaturatedhydrocarbons to carbonylic compounds which process employs noble metalcomponents but is not subject to the aforementioned disadvantages.

Accordingly, it is an object of this invention to provide a novelprocess for the preparation of car-bonylic compounds from ethylenicallyunsaturated hydrocarbons.

Another object of this invention is to provide a process for theselective conversion of ethylenically unsaturated hydrocarbons tocarbonylic compounds in the presence of contact agents that areextremely effective at relatively mild reaction conditions.

Another object of this invention is to provide a process for theconversion of ethylenically unsaturated hydrocarbons to carbonyliccompounds at relatively mild reaction conditions in the presence ofhighly active contact agents containing very small amounts of noblemetal components and thus obtaining a substantial economy in operationover prior art carbonylation processes employing substantial amounts ofnoble metal components.

Another object of this invention is to provide a novel process for theconversion of ethylenically unsaturated hydrocarbons to carbonyliccompounds at mild reaction conditions employing a contact agentcomprising two components which are ineffective when used separately atthese same mild reaction conditions.

Another object of this invention is to provide a liquid phase oxidationprocess for ethylenically unsaturated hydrocarbons using contact agentscontaining only very small amounts of noble metal components resultingin the avoidance of troublesome precipitation of insolubles which isoften associated with prior art liquid phase oxidation processesemploying noble metal components.

Still another object of this invention is to provide contact agentscomprising noble metal components and molybdenum trioxide orheteropolyacid components which contact agents enable the simple,economical, selective and direct conversion of ethylenically unsaturatedhydrocarbons to carbonylic compounds at relatively mild reactionconditions.

In accordance with this invention it has been found that ethylenicallyunsaturated hydrocarbons can be oxi dized to carbonylic compounds byexposing them to a supported or unsupported contact agent comprising (1)at least about 1%, by weight, of molybdenum trioxide or a heteropolyacidor salt thereof and (2) very small amounts, i.e. 1 1()- to about 3%, byweight, of platinum or palladium meta-ls or inorganic compounds of thesemetals, in the presence or absence of a gaseous oxidizing agent attemperature and pressure conditions more fully discussed hereinafter. Inthe absence of a gaseous oxidizing agent, the apparent action of thecontact agents disclosed herein is that of oxidant while, in thepresence of a .gaseous oxidizing agent it appears that their action isof a catalytic nature or a combination catalytic-oxidant nature.However, it should be understood that the invention is not limited toany particular explanation for the action of the agent and the termcontact agent is used to designate the particular reagents employed inthe process of this invention regardless of whether they act ascatalysts or oxidants or as both or in some other capacity, as isobvious to one skilled in the art.

The novel process of this invention is extremely elfective forcarbonylation of ethylenically unsaturated hydrocarbons alone or inadmixture, and particularly the monoethylenically unsaturatedhydrocarbons containing 2-10 carbon atoms. These ethylenicallyunsaturated hydrocarbons are converted to the corresponding carbonyliccompound containing the same number of carbon atoms in a simple,economic and direct manner. For example, ethylene is easily converted toacetaldehyde while styrene is easily converted to acetophenone. Thecomposition of the gaseous feed employed in the practice of thisinvention can be varied over a Wide range. Thus, when operating in acontinuous manner using oxygen in the feed, the amount of such oxygencan be varied over a wide range depending, for example, upon the designof equipment in use, the temperature, contact time, partial pressure ofother reactants, as is obvious to one skilled in the art. Theethylenically unsaturated hydrocarbons which can be employed in thepractice of this invention include, for example, ethylene, propylene,butene, hexene, heptene, octene, decene, dodecene, butadiene,pentadiene, cyclopen- 3 tcne, cyclohexene, styrene and the like. Totalconversion of such ethylenically unsaturated hydrocarbons can beincreased by recycling gaseous reaction product as a whole, or evenfurther, by separation and recycling of unreacted ethylenicallyunsaturated hydrocarbon.

As already indicated, the contact agents employed in the practice ofthis invention comprise at least two components, one of which ismolybdenum trioxide or a heteropolyacid or salt thereof, while the othercomponent of the contact agent contains platinum or palladium. It wasquite surprising that these two components could be combined to formcontact agents which can be used in liquid or solid form to oxidizeethylenically unsaturated hydrocarbons since either component of thecontact agent alone is ineffective under conditions where the totalcontact agent is extremely effective, as illustrated by working exampleswhich follow.

The molybdenum trioxide which can be used as one component of thecontact agent can be readily prepared from ammonium molybdate, forexample, by calcining this compound before or after inclusion into thecontact agent. In addition to, or as an alternative for, the molybdenumtrioxide, a heteropolyacid or salt of a heteropolyacid can also beemployed as one component of the contact agent. The structures of theheteropolyacids are difiicult to determine owing to the very large sizeof their molecules. However, the heteropolyacids may best be describedas complex inorganic substances of relatively high molecular weight inwhich two or more different acid cations or oxides of metals ormetaloids are associated with varying, frequently indeterminate amountsof combined water as water of hydration. The typical acid atom of theheteropolyacid, that is, the phosphorus atom in phos hoheteropolyacids,the silica atom in silicoheteropolyacids, etc., is regarded as thecentral atom of a nucleus. This central atom is hydrated and attached to6 oxygen atoms, thus H PO Hgsiog, etc. The oxygen appears to be linkedto the nuclear atom of phosphorus, silica, boron, arsenic or the like inthe same way that molecules of ammonia are bound to the metal atom inthe metallic amines. The oxygen atoms can be wholly or partiallysubstituted by radicals such as M M0 0 W0 W 0 V0 and V 0 Thus,phosphomolybdic acid, phosphotungstic acid, phosphovanadic acid and thelike can be formed. The

heteropolyacids or salts thereof form a well-known class of compoundsand include, for example, phosphomofybdic acid, silicomolybdovanadicacid, titanomolybdotungstic acid, silicornolybdic acid, germanomolybdicacid, chromimolybdic acid, stannotungstic acid, phosphotungstic acid,

cobalt phosphomolybdate, cadmium borotungstate, cadmium silicomolybdate,ferric silicomolybdate, ammonium vanadomolybdate, zinc phosphomolybdate,nickel stannotungstate, nickel silicotungstate, nickel borotungstate andthe like.

The second component of the contact agent is platinum or palladium metalor compounds of these metals. The platinum or palladium compoundsemployed are preferably inorganic compounds of platinum or palladium.However, complex palladium or platinum compounds containing an organicmoiety can be employed as long as such compounds are capable offurnishing a platinum or palladium atom to the contact agent in theamounts required. Thus, preferred classes of platinum or palladiumcornpounds include the halides, oxides, nitrates or sulfates of thesemetals. Suitable second components of the contact agent are exemplifiedby platinum metal, platinic chloride, platinic acid, 'chloroplatinicacid, platinic bromide, platinic hydride, platinic iodide, platinieoxide, platinic sulfate, platinic sulfide, platinous bromide, platinouschloride, platinous cyanide, platinous iodide, platinous oxide,palladium, palladous bromide, palladous chloride, palladous cyanide,palladic oxide, palladic sulfide, palladous hydroxide, palladous iodide,palladium monoxide, palladous sulfide, palladous nitrate, sodiumpalladous chloride, sodium, palladous sulfate and the organo-metulpalladium or platinum complexes formed with olefins, for example,ethylene as exemplified by PdCl C H complex or K(PtCl -C H Thecomponents of the contact agents can be combined in any suitable manneras is obvious to those skilled in the art, for example, where they areboth water soluble, the components are placed in distilled water andstirred and heated. A support can then be stirred into the solution andthe water evaporated.

he process of the invention can be carried out in either a liquid orvapor phase and the amounts of the components in the contact agents canbe varied over a wide range. For example, the content of the palladiumor platinum metal or compound of these metals can range from traceamounts, for example, as little as 1X 10 to as much as 3%, by weight,calculated as platinum or palladium, of the total dry weight of thecontact agent. In liquid phase particularly, satisfactory results can beobtained with as litte as l l0 'by Weight, of palladium or platinumcomponent while, in vapor phase, it is generally preferred to employ atleast .01%, by weight, of this component. Though the contact agents canbe used in unsupported form in vapor phase reaction, it is preferred touse them in supported form, i.e., on a carrier. When used in supportedform, the contact agents contain at least 1% and generally no more thanabout by Weight, of molybdenum trioxide, heteropolyacid or salt thereof,based on the total weight of the contact agent. It is particularlyadvantageous to employ contact agents containing from about 20% to about60%, by weight, of the molybdenum trioxide, heteropolyacid or saltthereof. Since the solubility of many of the heteropolyacids or theirsalts in aqueous medium is very high, a wide range in the concentrationof these materials in solutions is available for operation in the liquidphase. However, it is preferred to use concentrations of heteropolyacidsor their salts, and particularly phosphomolybdic acid or silicomolybdicacid, from about .005 molar to saturated solutions in water whenoperating the process of this invention in liquid phase. Molybdenumtrioxide can be used as a slurry in any practical proportion with theliquid when operating in liquid phase and in this case, highertemperatures and superatmospheric pressure may be used to increase therate of reaction. It is also possible to improve the action of thecontact agent by the incorporation of small amounts of hydrochloric acidor ferric chloride. Where hydrochloric acid is employed, it is used inconcentrations in the range of about .01 to about 3%, by weight, basedon the total weight of the contact agent, and ferric chloride can beused in mole ratios of iron to noble metals, i.e., platinum orpalladium, of up to about 10:1.

As already indicated, the contact agent can be employed in the processof this invention without being supported on a carrier. However, the useof a carrier has been found to be advantageous in the practice of theinvention, and it is preferred that such be used. Carriers that can beused to support the contact agent include any one or mixtures of theconventional carriers known in the art. All carriers, however, do notgive equivalent results and it is preferred therefore, that titania orsilica, for example, be used rather than alumina, for example. When asupport is employed it will generally be used with a surface area ofabout 8 to 200 sq. m./g. Suitable supports which can be employed in theprocess of this invention include, for example, silica, pumice,kies-elguhr, titania, alumina, silica alumina, zirconia, thoria, claysand silica gel.

Especially preferred among the contact agents of our invention are thesolid contact agents which contain (1) about 1% to about 90%, by weight,of a first component which is typically molybdenum trioxide, aheteropolyacid containing molybdenum, or a salt of a heteropolyacidcontaining molybdenum; (2) about 0.01% to about 3%, by weight, of asecond component which is platinum, palladium, or an inorganic compoundof platinum or palladium; supported on about 7% to about 99%,

by weight, of a support which contains at least a major amount, i.e.,more than 50%, by weight, of titania or zircoma.

Examples of the molybdenum-containing heteropolyacids of these preferredcontact agents include phosphomolybdic acid, silicomolybdic acid,chromimolybdic acid, germanamolybdic acid, cerimolybdic acid and othersmentioned hereinbefore.

Platinum chloride, platinum nitrate, palladium chloride, and palladiumnitrate are among the inorganic compounds of platinum or palladium whichare especially useful in these solid contact agents.

Typical of the supports which are especially useful in these solidcontact agents are titania or zirconia or mixtures containing a majoramount, i.e., more than 50%, of titania or zirconia and a minor amount,i.e., less than 50%, of silica.

The amount of the first component of these solid contact agentsgenerally exceeds the amount of the second component of the solidcontact agent by at least :1 and preferably by at least 30:1.

These solid contact agents preferably contain about to about 90%, byweight, of the first component and about 0.01% to about 3%, by weight,of the second component and, therefore, contain about 7% to about 80% ofthe support.

Especially preferred among these solid contact agents are those in whichthe first component is phosphomolybdic acid; the second component ispalladium chloride and the support is titania or titania with a minoramount.

of silica.

A factor having a significant influence on the course of the reactionforming the process of this invention is the use of a diluent orsolvent. Thus, the use of steam or liquid water as a diluent, eitheralone or in admixture with diluents such as nitrogen or other inertgases is particularly advantageous since, in their absence, the yield ofcarbonylic compound is reduced. In gas-phase reactions it is, of course,possible to use substances which are capable of producing water, forexample, hydrogen, rather than employing water directly.

The temperature at which the process of this invention is carried outcan be varied over a wide range. However, generally satisfactory resultsare obtained at temperatures in the range of about 100 to about 300 C.and preferably at temperatures from about 100 to about 225 C. in thevapor phase and from to about 170 C. in liquid phase. As is obvious toone skilled in the art, in order to obtain most selective reaction athighest yields of carbonylic compounds, care should be exercised toavoid temperatures above which substantial decomposition of reactant orproduct occurs. The pressures employed in the operation of thisinvention are also subject to wide variation, with pressures in therange of about 1 to about 100 atmospheres being generally satisfactoryand pressures in the range of about 1 atmosphere to about 5 atmospheresbeing preferred.

Any suitable reactor can be employed in carrying out the process of thisinvention and, for example, can be any one of several conventional typesusually employed in oxidation reactions for ethylenically unsaturatedhydrocarbons. Thus, the reactor can be a tubular type, fluidizedfixedbed, moving bed or other conventional type of reactor. It will be foundparticularly advantageous, however, to use apparatus permitting rapiddissipation of heat from the reaction Zone when the reaction is carriedout in the presence of oxygen or oxygen-containing gas in vapor phase.With continued use of the contact agent in such a reactor, the activitymay decrease. It has been found advantageous, therefore, to stop theflow of feed periodically and subject the contact agent to treatmentwith air or other oxidizing substance. This periodic regeneration can becarried out at the temperature of reaction or at a higher or lowertemperature, although ele vated temperatures are preferred. Thecarbonylic compounds prepared according to the process of this inventioncan be easily collected, for example, by condensation or washing out.The contact time, or the time in seconds a unit volume of the gaseousfeed mixture is in contact with a unit volume of contact agent atreaction temperature and pressure, can be varied within wide limits offrom about 0.1 second to about 100 seconds and preferably is in therange of about 1 second to about seconds depending upon the level ofconversion desired, operating temperature, feed composition, equipmentdesign, etc. Since reaction temperatures can vary considerably, thecontact time reported herein is at 100 C. and 735 mm. mercury pressure,unless otherwise indicated.

The excellent results obtained by the improved process of this inventionare readily appreciated from an examination of the examples that follow.The tubular Vycor reactor referred to in the following examples isconstructed of Vycor Glass and is cylindrical. The outer diameter of thecylindrical tube is 25 mm. and the length is 33 inches. Thefluidized-bed reactor referred to is also constructed of Vycor Glass andis cylindrical but with a conical bottom. The internal diameter of thelower portion is 40 mm. for 25 cm. of height and the upper portion ofthe reactor is mm. in diameter. The feed gases are directed into thebottom of the reactor serving to fiuidize the catalyst and the reactoris heated electrically. In the following examples, the compositions ofthe contact agents set forth are those that are calculated from theamounts of components used in their preparation. They are notnecessarily intended to represent the actual operating concentrations oreven the actual compounds present after use of the contact agents hasbegun.

This invention can be further illustrated by the following examples ofpreferred embodiments thereof although it will be understood that theseexamples are included merely for purposes of illustration and are notWise specifically indicated.

Example 1 As already indicated, carbonylic compounds can be preparedfrom the corresponding ethylenically unsaturated hydrocarbons usingcontact agents containing a platinum or palladium component and amolybdenum trioxide, heteropolyacid or heteropolyacid salt component. Toillustrate, a granular contact agent of 30%, by weight phosphornolybdicacid and .06% by Weight, of palladium chloride on titanium dioxide isheated to 155 C. in the tubular Vycor reactor described hereinbefore.The titani um dioxide support has a surface area of about 8.6 sq. m./ g.A gas feed containing 21% ethylene, 9% oxygen, and steam, by volume, ispassed through the reaction zone at a contact time of 7 seconds for aperiod of 30 minutes. The aqueous reaction product is condensed inreceivers coiled to 10 C. and C., respectively. Analysis of the productshows that 14.5% of the ethylene is converted to acetaldehyde and thespace-time yield. expressed as grams of acetaldehyde produced per literof contact agent per hour, is 22.7. The eflluent from the reactor issubstantially free of by-products, as shown by gas chromatography, forexample.

Repeating the above procedure after heating the contact agent in astream of air at 355 C., results in a conversion of ethylene toacetaldehyde of 16.8% and a space-time yield of 26.4. Thus, the activityof the contact agent can be increased by treating it in a stream of anoxygen-containing gas at an elevated temperature after it has once beenused.

Example 2 The individual components of the contact agents employed inthe process of this invention are not effective under mild conditions ofreaction when used separately. To illustrate, Example 1 is repeatedexcept that the contact agent contains only 30%, by weight,phosphomolybdic acid on the same titania support with the palladiumchloride being omitted. Upon analysis, the aqueous prod- '7 net of thisrun fails to show the presence of any carbonyl compound.

As a further illustration of this phenomena, Example 1 is repeated usinga contact agent containing only 0.06%, by weight, palladium chloride onthe same titania support, but omitting the phosphomolybdic acid. Theaqueous product from this run shows only a trace amount of acetaldehydewhen analyzed. Thus, the omission of either component from the contactagent employed. in the process of this invention results in a processwhich is essential ly inettective.

Example 3 Example 1 is repeated except that the phosphomolybdic acid andpalladium chloride are supported on titania having a surface area of1583 sq. m./g. and it is heated to 100 C. instead of 155 The run iscontinued for a period of 45 minutes and the conversion of ethylene toacetaldehyde during this time is 13% and the space-time yield is 20.3.

Example 4 The procedure of Example 1 is repeated at a temperature of 120C. using the contact agent from Example 3 after heating it in air at 350C. The duration of the run is 30 min. and the conversion of ethylene toacetaldehyde is 16% with a space-time yield of 25.2.

Example 5 A contact agent of 30%, by weight, phosphomolybdic acid and06%, by weight, palladium chloride supported on titania is placed in thereactor of Example 1 and heated to 147 C. A gas feed containing 30%ethylene and 70% steam, by volume, is passed through the reactor at acontact time of 9.5 seconds. After 30 min. the conversion of ethylene toacetaldehyde amounts to 8.9% and the space-time yield is 14.

Example 6 The process of this invention can be carried out in afluidized-bed reactor. Thus, a contact agent of 30%, by weight, ofphosphomolybdic acid and .06%, by weight, of palladium chloride ontitania is heated to 126 C. in the fluidized-bed reactor describedhereinabove. A gas feed containing 21% ethylene, 9% oxygen and 70%steam, by volume, is passed through the bed at a contact time of 4-seconds to impart a fluid motion to the particles. During a period of 30minutes the aqueous product collected shows a conversion of ethylene toacetaldehyde of 8.1% and a space-time yield of 21.3.

Example 7 Granular contact agent of 30%, by weight, phosphomolybdic acidand 06%, by weight, of palladium chlo ride on titania is packed into thetubular Vycor reactor. While heated to a temperature of 147 C., thecontact agent is exposed to a gas feed containing 21% ethylene, 9%oxygen and 70% steam, by volume, at a contact time of 1.3 seconds. Theduration of the run is 30 minutes and the conversion to acetaldehyde is7.6% and the spacetime yield is 59.7.

Repeating this run with a contact agent containing .18%, by weight, ofpalladium chloride rather than 06% palladium chloride, the conversion ofethylene to acetaldehyde is 9.6% and the space-time yield is 73.6.

Example 8 As indicated hereinbefore, inert gases such as nitrogen can bemixed with steam and the mixture used as diluent in the process of thisinvention. Thus, the procedure of Example 1 is repeated using a gas feedcontaining 10.2% ethylene, 2.2% oxygen, 70% steam and 17.6% nitrogen, byvolume, at a temperature of 123 C. and a contact time of 3.2 seconds.The aqueous reaction product collected during 30 minutes of operationshows that 18.2% of the ethylene is converted to acctaldehyde with aspacetime yield of 28.6.

Example 9 Example 10 The procedure of Example 1 is repeated using a gasfeed containing 52.6% propylene, 35.1% oxygen, 8.8% steam and 3.5%nitrogen, by volume, at a temperature of 220 C. and a contact time of5.3 seconds. In a run lasting for 30 minutes the conversion of propyleneto acrolein is 4% and the space-time yield is 25.1.

Example 11 Using the procedure of Example 1, a contact agent of 58.5%phosphomolybdic acid, .05%, by weight, palladium chloride on silica isreacted with the gas feed of Example 1 at 123 C. and a contact time of 7seconds. During 30 minutes of operation the conversion of ethylene toacetaldehyde is 14% and the space-time yield is 22.0.

Example 12 The procedure of Example 1 is repeated except that thesupport is zirconia and the contact agent is heated to a temperature of148 C. The conversion of ethylene to acetaldehyde is 8.5% and thespace-time yield is 13.3 in a run of 30 minutes duration.

Example 13 Example 1 is repeated except that the support issilicaalumina instead of titania and the contact agent is heated to 120C. before contacting it with the gas feed. During 30 minutes theconversion of ethylene to acetaldheyde is 4.3% and the space-time yieldis 6.7.

Example 14 The procedure of Example 1 is repeated using a contact agentcontaining 30%, by Weight, phosphomolybdic acid and .13%, by weight, ofplatinic chloride on titania. The contact agent is exposed to the gasfeed of Example 1 while heated to 147 C. at a contact time of 7 seconds.The conversion of ethylene to acetaldehyde is 2.8% and the space-timeyield is 4.4 in a run of 30 minutes duration.

Example 15 Different types of reactors can be employed in carrying outthe process of this invention and such process can be carried out inliquid or vapor phase. When operating in liquid phase, contact agentsusing very small amounts, e.g. 1 10- by weight, of platinum or palladiumcomponents are generally employed. Thus, ethylene is introduced througha fritted thimble at the bottom of a reactor made from a length of 38mm. outer diameter Pyrex tubing 8 inches in length, which is packed withinch ceramic saddles. The tube contains an aqueous solution which is .1molar in phosphomolybdic acid and 1 10- molar in palladium chloride. Thesolution is heated to approximately 90 C. and, on initial contact withthe ethylene at an input rate of 48 ml. of ethylene per ml. of solutionper hour, the contact agent turns green. With continued exposure thecontact agent turns deep blue. The aqueous reaction product is collectedby passing the efiluent from the reactor through traps cooled to 10 and80 C. res ectively. During a run of minutes duration 11.5% of theethylene is converted to acetaldehyde and the effluent from the reactoris substantially free of by-product. No evidence of the precipitation ofsolids from the contact agent couid be detected following its use.

The contact agents employed in the process of this invention can beregenerated after use. Thus, the contact agent employed in this exampleis regenerated by dispersed gaseous perchloroylfluoride through thesolution after flushing out residual ethylene and acetaldehyde. When theabove procedure is repeated, following such regeneration, essentiallythe same results in acetaldehyde production are obtained.

As in the vapor phase operation of the process of this invention, thetwo components of the contact agent must also be present in the liquidphase in order to have a truly effective contact agent. Thus, omissionof the palladium chloride in the above procedure results in no aldehydebeing prepared and when the phosphomolybdic acid is omitted only traceamounts of carbonyl compound are detected in the initial reactionefiiuent following which, no reaction is observed.

When the procedure of this example is repeated using butene-l, or amixture of cis and trans butene-2 rather than ethylene, there isobtained ethyl methyl ketone substantially free of by-products.Furthermore it is possible to substitute silicomolybdic acid for thephosphomolybdic acid or chloroplatinic acid for palladium chloride andobtain similar results.

Example 16 The procedure of Example is repeated except that proylene isintroduced into the reactor instead of ethylene. The effluent from thereactor contains acetone substantialy free of by-products. Thus, it canbe seen by comparison of this example with Example 10 that differentcarbonylic compounds can be prepared from the same ethylenicallyunsaturated hydrocarbon by varying reaction conditions, for example,temperature.

Example 17 The procedure of Example 7 is repeated except that thecontact agent is by weight, phosphomolybdic acid and .13%, by weight, ofpalladium nitrate on titania. The conversion of ethylene to acetaldehydeis 10.1% and the space-time yield is 79.2 for a run of 30 minutesduration.

Example 18 The procedure of Example 7 is repeated except that thecontact agent is 30%, by weight, silicomolybdic acid and .06%, byweight, palladium chloride on titania. In a run of 30 minutes duration,the conversion to acetaldehyde is 7.8% and the space-time yield is 61.

Example 19 As indicated hereinbefore, the contact agent can also containferric chloride. To illustrate, the procedure of Example 7 is repeatedexcept that the contact agent is 30%, by weight, of phosphomolybdicacid, .06%, by weight, of pallidum chloride and .18% ferric chloride ontitania. The conversion of ethylene to acetaldehyde is 12.6% and thespace-time yield is 99.2 for a run of 30 minute duration.

Example 20 As pointed out hereinbefore, certain of the carriers orsupports are preferred over others. Particularly advantageous resultscan be achieved using titania gel made by precipitation of the oxidefrom aqueous titanium tetrachloride with ammonia. Repeating theprocedure of Example 7 using this particular support the conversion ofethylene to acetaldehyde is 11% and the space-time yield is 86.6.

Example 21 Molybdenum trioxide is an effective component in the contactagent employed in the process of this invention. To illustrate, Example7 is repeated except that the contact agent is 21.9%, by weight,molybdenum trioxide and .06%, by weight, of palladium chloride ontitania having a surface area of approximately 200 sq. m./g. In a run of30 minutes duration the conversion of acteladehyde is 6.1% and thespace-time yield is 48.

Example 22 The phosphomolybdic acid can be formed in situ in preparingthe contact agent of this invention. Thus, Example 1 is repeated exceptthat the contact agent is 21.9%, by weight, molybdenum trioxide, 1.24%,by weight, phosphoric acid and .06%, by weight, palladous chloride ontitania having a surface area of 7.1 sq. m./ g. The atomic ratio ofmolybdenum to phosphorous is 12:1. In a run lasting 30 minutes theconversion to acetaldehyde is 18.8% and the space-time yield is 29.5.

Repeating the above run with a contact agent of 21.9%, by weight,molybdenum oxide, .62%, by weight, phosphoric acid and 0.6%, by weight,of palladous chloride on titania, there is obtained a conversion toacetaldehyde of 16.0% and a space-time yield of 25.0.

When the above run is repeated using a contact agent of 21.9%, byweight, molybdenum oxide, 2.48%, by weight, phosphoric acid and .06%, byweight, of palladous chloride on titania the conversion to acetaldehydeis 15.1% and the space-time yield is 23.8.

Example 23 A contact agent of 30%, by weight, phosphomolybdic acid and0.1%, by weight, palladous chloride is prepared by dissolving 30 g. ofphosphomolybdic acid and mg. of palladous chloride in 50 ml. ofdistilled water with stirring and heating. The amber-colored solution isstirred into a mixture of 69.9 g. of titania and the paste thickened byevaporation of the water. The preparation is then dried for a period of15 hours at a temperature of 145 C., cooled in a desiccator and a -4+20mesh component screened out, 50 ml. of this contact agent is packed intothe Vycor reactor described hereinbefore. During 30 minutes at a furnacetemperature of 148 C. the contact agent is exposed to a gas feedcontaining .089 mole of ethylene, 0.038 mole of oxygen and 0.297 mole ofsteam. Analysis of the aqueous reaction product collected as in Example1 shows .016 mole of acetaldehyde corresponding to aconversion of 18%and a space-time yield of 28.2.

Example 24 As already indicated, the materials employed as supports forthe contact agent of this invention can be used alone or in admixture. Aparticularly good mixture for this purpose is a mixture of titania andsilica. Thus, a contact agent of 30%, by weight, phosphomolybdic acid,.1%, by weight, palladous chloride, 48.9% titania and 21% silica isemployed in a fluid-bed reactor, as described above. The gas feedcontains 14.6% ethylene, 65.2% steam and 20.2% air, by volume, at areactor temperature of C. and a contact time of 0.9 second. The runlasts 60 minutes and the conversion to acetaldehyde is 11.8% and thespace-time yield is 95.4.

Thus, by the practice of this invention there is provided a simple,economical and direct process for the conversion of ethylenicallyunsaturated hydrocarbons to carbonylic compounds containing the samenumber of carbon atoms. The carbonylic compounds prepared by the processof this invention can be used for a wide variety of solvent extractionpurposes as well as intermediates in the preparation of many usefulorganic compounds. For example, acrolein which can be prepared from theoxidation of propylene using the process of this invention is awell-known compound which is extensively used in the preparation of wargases, resins, glycerin, polyurethane, polyester resins, methionine andpharmaceuticals.

Although the invention has been described in considerable detail withreference to certain preferred embodiments thereof, it will beunderstood that variations and modifications can be effected withoutdeparting from the spirit and scope of the invention as describedhereinabove and as defined in the appended claims.

We claim:

1. .A solid contact agent for promoting the oxidation of ethylenicallyunsaturated hydrocarbons to carbonylic compounds consisting essentiallyof (1) about 1% to about 90% by weight, of a first component selectedfrom the group consisting of:

(a) molybdenum trioxide, (b) a molybdenum containing heteropolyacid,

and (c) a salt of a molybdenum containing heteropolyacid; (2) about0.01% to about 3% by weight of a second component selected from thegroup consisting of;

(a) metallic platinum, (b) metallic palladium, and (c) a compound ofplatinum or palladium; supported on about 7% to about 99% by weight of asupport which contains at least a major amount of a component selectedfrom the group consisting of:

(a) titania, and (b) zirconia;

wherein the amount of said first component is at least 15 times as greatas the amount of said second component.

2. A contact agent according to claim 1 in which the first component isselected from the group consisting of:

(a) phosphomolybdic acid,

(b) silicomolybdic acid,

(c) a salt of phosphomolybdric acid, and

(d) a salt of silicomolybdic acid.

3. A contact agent according to claim 1 in which said second componentis selected from the group consisting of:

(a) metallic platinum,

(b) metallic palladium,

(c) platinum chloride,

(d) platinum nitrate,

(e) palladium chloride, and

(f) palladium nitrate,

4. A contact agent according to claim 1 in which said support contains aminor amount of silica.

5. A contact agent according to claim 1 consisting essentially of (1)about 20% to about 90% by weight of said first component; (2) about0.01% to about 3% by weight of said second component; and about 7% toabout 80% by weight of said support; wherein the amount of said firstcomponent is at least 30 times as great as the amount of said secondcomponent.

6. A contact agent according to claim in which the first component isselected from the group consisting of:

(a) phosphornolybdic acid,

(b) silicomolybdic acid,

(c) a salt of phosphomolybdic acid, and

(d) a salt of isilicomolybdic acid.

7. A contact agent according to claim 5 in which said second componentis selected from the group consisting of:

(a) metallic platinum,

(b) metallic palladium,

(c) platinum chloride,

(d) platinum nitrate,

(e) palladium chloride, and

(f) palladium nitrate.

8. A contact agent according to claim 5 in which said support contains aminor amount of silica.

9. A contact agent according to claim 5 in which said first component isselected from the group consisting of:

(a) phosphomolybdic acid,

(b) silicomolybdic acid,

(c) a salt of phosphomolybdic acid, and

(cl) a salt of silicomolybdic acid;

said second component is selected from the group consisting of:

(a) metallic platinum,

(b) metallic palladium,

(c) platinum chloride,

(d) platinum nitrate,

(e) palladium chloride, and

(f) palladium nitrate;

and said support is selected from the group consisting of:

(a) titania,

(b) zirconia,

(c) titania and a minor amount of silica, and

(d) zirconia and a minor amount of silica.

10. A contact agent according to claim 9 in which said first componentis phosphomolybdic acid; said second component is palladium chloride andsaid support is selected from the group consisting of z (a) titania, and

(b) titania and a minor amount of silica.

References Cited UNITED STATES PATENTS 2,317,683 4/1943 Greensfelder252470 2,608,534 8/1952 Fleck 252-47O 2,650,906 9/1953 Engel et a1252-470 3,094,493 6/1963 Nixon 252466 3,153,678 10/1964 Logemann 252470DANIEL E. WYMAN, Primary Examiner.

PATRICK P. GARVIN, Examiner.

L. G. XIARHOS, L. G. MANDONI, Assistant Examiners.

Edward M. Fletcher, J r.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,379,651 April 23, 1968 Charles Wesley Hargis et a1.

It is certified that error appears in the above identified patent andthat said Letters Patent are hereby corrected as shown below:

In the heading to the p inted specification, line 6, "P. 0

Box 511, Kingsport, Tenn. 3 662" should read Kingsport, Tenn. assignorsto EastmaniKodak Company, Rochester, N.

a corporation of New Jersey] Signed and sealed this 23rd day ofSeptember 1969.

(SEAL) Attest:

WILLIAM E. SCHUYLER'F'YJR.

Commissioner of Patents Attesting Officer

